Phosphoric acid phenylsulphonamide esters

ABSTRACT

Phosphoric acid phenylsulphonamide esters of the formula WHEREIN Y represents oxygen or sulphur, R represents alkyl with 1 to 5 carbon atoms, R1 represents alkyl with 1 to 5 carbon atoms, alkenyl and alkinyl each with 3 to 5 carbon atoms, alkoxyalkyl with 1 to 5 carbon atoms in each of the moieties, alkylthioalkyl with 1 to 5 carbon atoms in each of the moieties, or haloalkyl with 1 to 5 carbon atoms, R2 represents hydrogen, alkyl with 1 to 5 carbon atoms or alkenyl with 3 to 5 carbon atoms, R3 represents hydrogen and X and X1 each represents halogen or alkyl with 1 to 5 carbon atoms, or R3 represents alkyl with 1 to 5 carbon atoms and X and X1 each represents hydrogen, halogen or alkyl with 1 to 5 carbon atoms, a process for their manufacture and their use in pest control.

States Patent [1 1 Drabek et a1.

[1 11 3,855,362 [451 Dec. 17, 1974 1 1 PHOSPHORIC ACID PHENYLSULPHONAMIDE ESTERS [75] Inventors: Jozef Drabek, Allschwil; Denis Varsanyi, Arlesheim, both of Switzerland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22] Filed: Nov. 29, 1972 [21] Appl. No.: 310,507

[30] Foreign Application Priority Data OTHER PU BLICATIQNS Wagner et al., J. Med. Chem., 8(3), 1965, pages 377 to 383.

Primary I5.ran1itwr-Lorraine A. Weinberger Assistant ExaminerRichard L. Raymond Attorney, Agent, or Firm-Harry Falber; Frederick H. Rabin 5 7 ABSTRACT Phosphoric acid phenylsulphonamide esters of the formula X R R0 Y 1 SO N 2 P O I R R 8 wherein Y represents-oxygen or sulphur, R represents alkyl with 1 to 5 carbon atoms, R represents alkyl with 1 to 5 carbon atoms, 'alkenyl and alkinyl each with 3 to 5 carbon atoms, alkoxyalkyl with 1 to 5 carbon atoms in each of the moieties, alkylthioalkyl with 1 to 5 carbon atoms in each of the moieties, or haloalkyl 1 with 1 to 5 carbon atoms, R represents hydrogen, alkyl with l to 5 carbon atoms or alkenyl with 3 to 5 carbon atoms, R represents hydrogen and X and X each represents halogen or alkyl with 1 to 5 carbon atoms, or R represents alkyl with 1 to 5 carbon atoms and X and X each represents hydrogen, halogen or alkyl with 1 to 5 carbon atoms, a process for their manufacture and their use in pest control.

12 Claims, No Drawings PHOSPHORIC ACID PHENYLSULPHONAMIDE Y ESTERS I t The present invention relates to phosphoric acid phenylsulphonamide esters, a process for their manufacture and their use in pest control.

The compounds having the formula wherein Y represents oxygen or sulphur, R represents 7 alkyl with l to 5 carbon atoms, R represents alkyl with l to 5 carbon atoms, alkenyl and alkinyl each with 3 to 5 carbon atoms, alkoxyalkyl with 1 to 5 carbon atoms in each of the moieties, alkylthioalkyl with l to 5 carbon atoms in each of the moieties, or haloalkyl with l to 5 carbon atoms, R represents hydrogen, alkyl with l to 5 carbon atoms or alkenyl with 3 to 5 carbon atoms, R represents hydrogen and X and X, each represents halogen or alkyl with l to 5 carbon atoms, or R represents alkyl with l to 5 carbon atoms and X and Y R u j 1) P-Cl v H .R s j I (II) (III) Y R u P-Cl (II) (IV) Y IX R2 5a) R u SO2N X each represents hydrogen,- halogen or alkyl with 1 to 5 carbon atoms.

Halogen is to be understood as meaning fluorine,

chlorine, bromine or iodine, but in particular chlorine. Preferred haloalkyl groups with l to 5 carbon atoms The groups cited hereinabove which are possible for .R to R X and X,, may be straight-chain or branched.

Examples of such groups include: methyl, methoxy, methoxymethyl, ethyl, ethoxyethyl, ethylthioethyl, propyl, isopropyl, n-, i-, sec. and tert.butyl, n-pentyl and the isomers thereof, allyl, methallyl, n-penten-S-yl, propargyl, isobutinyl.

Preferred compounds on account of their action are those of the formula l, wherein R represents methyl or ethyl, R, represents propyl, n-butyl, n-pentyl or C H OCH CH R represents hydrogen, methyl or ethyl, R represents methyl or ethyl, X and X, each represents hydrogen or chlorine, and Y represents oxygen or sulphur.

Particularly preferred compounds, however, are those of the formula I, wherein R represents ethyl, R

represents propyl, n-butyl, C H OCH Cl-l or n-amyl,

R and R each represents methylor ethyl, X and X represent hydrogen or chlorine and Y represents oxygen. I

The compounds of the formula I can be manufactured according to methods'which are known per se:

SO N

- acid binding X I 4 agent.

reaction temperature 0-12O C MeSH reaction temperature 0-100C essary to use catalysts in the reactions, e.g. copper or copper chloride.

Processes l, 2, 3a and 3b may be carried out at normal pressure (3a at up to atmospheres absolute pressure) and in solvents or diluents. Suitable solvents or diluents are e.g., ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dioxan, dimethoxyethane, tetrahydrofu'ran; amides, such as N,N-

, dialkylated carboxylic amides; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylenes, chloroform, chlorobenzene; nitriles, such as acetonitrile; dimethyl sulphoxide, ketones such as acetone, methyl ethyl ketone.

Some of the starting materials of the formulae II and V are known compounds which can be manufactured in analogous manner by known methods. The compounds of the formula I display a broad biocidal activity and are therefore suitable for combating various plant and animal pests and as plant growth regulators. Surprisingly, however, the compounds of the formula possess insecticidal and acaricidalt properties which are superior to those of know, analogous compounds, and they may be used against all development stages, e.g., eggs, larvae, pupae, nymphs and addults, of insects and representatives of the order Acarina, for example against insects of the families:

'letligonidae Tenebriomkiae Gryllidae Chrysomelidae Gryllotalpidae Bruchidag Blallidae Tineidae Reduviidae Notlindae Phyrrhoconae Lymarriidae Cimicidae Pyralidae Delphacidae Culicidae Alphididae Tipulidae Diaspididae Slamoxydae Pseudococcidae Tryperidae Scarabaeidae Muscidae Dermesridae Calliphoridae and Coccinellidae Pulicidae Acarida of the families:

Ixodidae .Argasidae Tetranychidae and Dermanyssidae.

for example, the following Z-methoxycarbamyll -methylvinyldimethylphosphate (MEVINPHOS) Dimethyll -methyl-2-( methylcarbamoyl vinylphosphate cis (MONOCROTOPHOS) 3-(dimethoxyphosphinyloxy)-N,N-dimethyl-ciscrotonamide (DlCROTOPHOS) 2-chloro-2-diethylcarbamoyl-l-methylvinyldimethylphosphate (PHOSPHAMIDON) 0,0-diethyl-O(or S)-2-(ethylthio)-ethylthiophosphate (DEMETON) S-ethylthioethyl-0,0-dimethyl-dithiophosphate (THI- OMETON) 0,0-diethyl-S-ethylmercaptomethyldithiophosphate (PHORATE) 0,0-diethyl-S-Z-ethylthio)ethyldithiophosphate SULFOTON) 0,0-dimethyl-S-2-(ethylsulphinyl)ethylthiophosphate (OXYDEMETONMETHYL) 0,0-dimethyl -S-( l ,2-dicarbethoxyethyldithiophosphate (MALATHION) 0,0,0,0-tetraethyl-S,S'-methylene-bisdithiophosphate ETHlON) O-ethyl-S,S-dipropyldithiophosphate 0,0-dimethyl-S-(N-methyl-N- formylcarbamoylmethyl)-dithiophosphate MOTHlON) 0,0-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate (DlMETHOATE) I 0,0-dimethyl-O-p-nitrophenylthiophosphate RATHlON-METHYL) 0,0-diethyl-O-p nitrophenylthiophosphate (PARA- THlON) O-ethyl-O-pmitrophenylphenylthiophosphate (EPN) 0,0-dimethyl-O-(4-nitro-m-tolyl)thiophosphate (FENlTROTHlON) 0,0-dimethyl-O-Z,4,-5-trichlorophenylthiophosphate- (RONNEL) O-ethyl-O,2,4,5-trichlorophenylethylthiophosphate (TRICHLORONATE) (FOR- 0,0-dimethyl-O-2,5-dichloro-4-bromophenylthiophos-- phate (BROMOPHOS) 0,0-dimethyl-O-(2,5-dichloro-4-jodphenyl)- thiophosphate (JODOFENPHOS) 4-tert. butyl-2-chlorophenyl-N-methyl-O- methylamidophosphate (CRUFOMATE) 0,0-dimethyl-O-(3-methyl-4-methylmercaptophenyl)- thiophosphate (FENTHION) lsopropylarnino-O-ethyl-O'(4-methylmercapto-3- methylphenyl)-phosphate 0,0-diethyl-O-p-(methylsulphinyl)phenylthiophosphate (FENSULFOTHION) O-p-(dimethylsulphamid0)phenyl-0,0-dimethylthiophosphate (FAMPHUR) 0,0,0,O'-tetramethyl-0,0'-thiodi-p-phenylenethiophosphate O-ethyl-S-phenyl-ethyldithiophosphate 0,0-dimethyl-O-( oz-methylbenzyl 3-hydroxycrotonyl phosphate 2-chloro-1-(2,4-dichl0rophenyl)vinyldiethylphosphate (CHLORFENVINPHOS) dimethylphosphate O-[2-chloro l-(2,5-dichlorophenyl)]vinyl-0,0-

diethylthiophosphate Phenylglyoxylonitriloxium-0,0-diethylthiophosphate PHOXIM) 0,0-diethyl-O-(3-chloro-4-methyl-2-oxo-2-H-I- 2-( l-methoxy-2-propoxy)pheny-N-methylcarbamate 9 2-( 1,3-dioxolan-2-yl )phenyl-N,N-dimethylcarbamate 2-( 1,3-dithiolan-2-yl)-N,N-dimethylcarbamate 2-( l,3-dithiolan-2yl)phenyl-N,N-dimethylcarbamate 2-isopropoxyphenyl-N-methylcarbamate (APROCARB) 2-(Z-propinyloxy)phenyl-N-methylcarbamate 3-( 2-propinyloxy )phenyl-N-methylcarbamate Z-dimethylaminophenyl-N-methylcarbamate 2-diallylaminophenyl-N-methylcarbamate 4-diallylamino-3,5-xylyl-N-methylcarbamate LYXlCARB) 4-benzothienyl-N-methylcarbamate 2,3-dihydro-2-methyl-7-benzofuranyl-N- methylcarbamate 3-methyll -phenylpyrazol-5-yl N,N-dimethylcarbamate l-isopropyl-3-methylpyrazol-5-yl-N,N,-dimethylcarbamate (ISOLAN) 2-dimethylamino-5,6-di methylpyrimidine-4-yl-N,N,- dimethyl-carbamate 3-methyl-4-dimethylaminomethyleneiminophenyl-N- methylcarbamate 3-dimethylamino-methyleneiminophenyl-N- methylcarbamate (FORMETANATE) and their salts l-methylthio-ethylimino-N-methylcarbamate (ME-- THOMYL) 2-methylcarbamoyloxirnino-l ,3-dithiolane 5-methyl-2-methylcarbamoyloximino-1,3-oxythiolane 2-( lbutin-3-yl-oxy)phenyl-N-methylcarbamate l-dimethylcarbamyl-1methylthio-O-methylcarbamylformoxime l-( 2-cyanoethylthio )-O-methylcarbamylacetaldoxime. 1 -methylthio-O-carbamyl-acetaldoxime O-( 3-sec.butylphenyl)-N-phenylthio-N- methylcarbamate 2,5-dimethyl-l ,3-dithioland-2-(O-methylcarbamyl)- aldoxime 0-2-diphenyl-N-methylcarbamate 2-(N-methylcarbamyl-bximino)-3chlorobicyclo[2.2.1]heptane 2-(N-methylcarbamyl-oximino)-bicyclo[2.2. l ]heptane 3-isopropylphenyl-N-methyl-N-chloroacetylcarbamate 2[dipropargylamino]-phenyl-N-methylcarbamate 4[dipropargylamino ]-3-tolyl-N-methylcarbamate 4[dipropargylamino]-3,5-xylyl-N-methylcarbamate 2-[allyl-isopropylamino]-phenyl-N-methylcarbamate 3-[ally-isopropylamino]-pheny-N-methylcarbamate Chlorinated Hydrocarbons 'y-hexachlorocyclohexane lGAMMEXANE; LlNDAN; yHCH] l,2,4,5,6,7,8,8-octachloro-3a,4,7,7atetrahydro-4,7-

' methylen-indane [CHLORDAN] l,4,5,6,7,8,8-heptachloro,3a,4,7,7a-tetrahydro-4,7- methylen-indane [HEPTACHLOR] l,2,3,4,10,lO-hexachloro-l,4,4a,5,8a-hexahydroendol ,4-exo-5,S-dimethanonaphthalene [ALDRIN] 1,2,3 ,4, l 0, l O-heXachloro-6,7-epoxyl ,4,4a5,6,7,8,8a-

oxtahydro-exo-l ,4-endo-5 ,Sdimethanonaphthalene [DIFLORIN] l,2,3,4,1O,IO-hexachloro-SJ-epoxy l,4,4a,5,6,7,8,8aoctyhydro-endo-endo-S,8-dimethanonaphthalene [EN- N] The active substances of the formula I are also suitable for combating representatives of the division Thallophyta, e.g., viruses, bacteria and fungi. They thus possess fungicidal properties against phytophathogenic fungi on various cultivated plants, such as cereals, maize, rice, vegetables, ornamental plants, fruit trees, vines, farms products, etc.

With the new active substances it is possible to con trol or destroy fungi occurring onfruit, blossom, leaves,

stems, tubers and roots, and from which parts of plants which grow later then also remain free. The active sub stances of theformula I are active in particular against phytopahtogenic fungi belonging to the following classes: Oomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Denteromycetes.

In addition, the new active substance can also be used for treating seeds, fruits, tubers etc., and the protecting them from fungus infections, for example from smut fungi of all kinds, such as Ustilaginales, e.g. Ustilago, Tilletia, Urocystis, Turbicinia and Phoma types.

In addition to the above cited acaricides and insecti-- cides, it is also possible to admix' the active substances of the formula I with, for example, batericides, fungi- I static agents, baceteriostatic agents, nematocides andthe activity spectrum: dodecylquanidine acetate (DODlNE) (CHLOR- N'-dichlorofluoromethylthio-N,N-dimethyl-N'- phenylsulfamide (DICHLOFLUANID) O-ethyl-S-benzyl-phenyldithiophosphate 0,0-diethyl-S-benzyl-thiolphosphate disodium-ethylene-1,2-bis-dithiocarbamate (NABAM) zinc-ethylenel ,2-bis-dithiocarbamate (ZINEB) manganese-ethylene-l ,2-bis-dithiocarbamate meric) (MANEB) tetramethyliuramdisulfide (THIRAM) l -oxy-3-acetyl-6-methyl-cyclohexene-( 5 )dione-( 2,4) (DEHYDROACETIC ACID) 8-hydroxyquinoline (8-QUINOLINOL) 3O 2-dimethylamino-6-methyl 5-n-butyl-4-hydroxyprimidine methyl-N-benzimidazole-2yl-N-(butylcarbamoyl)carbamate (BENOMYL) 2-ethylamino-6-methyl-5n-butyl-4-hydroxypyrimidine 2,3-dicyano-1,4-dithia-anthraquinone (DITHIANON 2-(4-thiazolyl)-benzimidazole 3 ,S-dimethyltetrahydro-l ,3 ,5'-thiadiazine-2-thione (DAZOMET) 2,3-dihydro-5-carboxanilido-6-inethyll ,4-oxathine 40 pentachlorobenzyl alcohol.-

Furthermore, the compounds of the formula I are suitable for combating plant pathogenic nematodes.

The compounds of the formula I may be used as pure active substance or together with suitable carriers and- /or additives. Suitable carriers and additives can be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.

'For application, the compounds of the formula I may be processed to dusts, emulsion concentrates, granules, dispersions, sprays, to solutions, or suspensions in the conventional formulation which is commonly employed in application technology. Mention may also be made of cattle clips and spray races," in which aqueous preparations are used.

The agents according'to the invention are manufactured in known manner by intimately mixing and/or grinding active substances of the formula I with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substances. The active substances may take and be used in the following forms:

Solid forms:

Dusts, tracking agents, granules, coated granules, impregnated granules and homogeneous granules.

Liquid forms:

a. active substances which are dispersible in water:

wettable powders, pasts, emulsions;

b. solutions.

To manufacture solid forms (dusts, tracking agents), the active substances are mixed with solid carriers. Suitable carriers are, for example, kaolin, talcum, bo- Ius, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminium silicates (feldspar and mica), calcium and magnesium sulphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc. These substances can either be used alone or in admixture with one another.

Granules can be very easily manufactured by dissolving an active substance of the formula I in an organic solvent and applying the resulting solution to a granulated material, for example attapulgite, S10 granicalci um, bentonite etc. and then evaporatingthe solvent. v

Polymer granules can also be manufactured by mixing the active substances of the formula I with polymerisable compounds (urea/formaldehyde; dicyandiamide/formaldehyde; melamine/formaldehyde or others), whereupon a mild polymerisation is carried out that does not affect the active substances and in the process of which the granulation is carried out during the gel formation. It is more advantageous to impregnate finished, porous polymer granules (urea/formaldehyde, polyacrylonitrile, polyester or others) which have a specific surface area and a favourable predeterminable adsorption/desorption ratio, with the active substances, for example in the form of their solutions (in a low boiling solvent) and to remove the solvent. Polymer granules of this kind in the form of microgranules having a bulk density of 300 g/litre to 600 g/litre can also be manufactured with the aid of atomisers. The dusting can be carried out from aircraft over extensive areas of cultures of useful plants.

It is also possible to obtain granules by compacting the carrier with the active substance and carriers and subsequently comminuting the product.-

To these mixtures can also be added additives which stabilize the active substance and/or non-ionic, anionic and cationic surface active substances, which, for example, improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and a dispersibility (dispersing agents). Examples of suitable adhesives are the following: olein/chalk mixture, cellulose derivates (methyl cellulose, carboxy methyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulphonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moi ety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e., wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substanceand anti-foam agents and, optionally, solvents.

W'ettable powders and pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulentcarriers in suitable apparatusuntil homogeneity is attained. Suitable carriers are, for example, those mentioned for the solid forms of application. In some cases it is advantageous to use mixtures of different carriers. As dispersing agents there can be used, for example, condensation products of sulfonated naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, as well as alkali, ammonium and alkaline earth metal salts of lignin sulfonic acid, in addition, a]-

kylaryl sulfonates, alkali and alkaline-earth metal salts of dibutyl naphthalene sulfonic acid, fatty alcohol sulfates such as salts 'of sulfated hexadecanols, hep- 'tadecanols, octadecanols, and salts of sulfated fatty alcohol glycol ethers, the sodium salt of oleoyl ethionate, the sodium salt of oleoyl methyl tauride, ditertiary acetylene glycols, dialkyl fatty acid alkali and alkaline earth metal salts.

Suitable anti-foam agents are silicones. g

The active substances are mixed, ground, sieved and strained with the additives cited hereinabove in such a. manner that, in wettable powders, the solid particle size of from 0.02 to 0.04 and in pastes, of 0.03 is notexdilauryl ammonium chloride and ceeded. To produce emulsifiable concentrates and pastes, dispersing agents such as those cited above,-organic solvents and water are used. Examples of suitable solvents are: alcohols, benzene, xylene, toluene dimethyl sulfoxide, and mineral oil fractions boiling between 120 and 350C. The solvents must be practically odourless, not phytotoxic, inert to the active substances.

Furthermore, the agents according to the invention can be applied in the form of solutions. For this purpose the active substance or several active substances of the general formula I are dissolved in suitableorganic solvents, mixtures of solvents or in water. Aliphatic and aromatic hydrocarbons, chlorinated derivatives thereof, alkyl naphthalenes, and mineral oils singly or in admixture with each other, can be used as organic solvents.

The content of active substance in the above described agents is between 0.1 to 95 percent, in which connection it should be mentioned that, in the case of application from aircraft or some other suitable means of application, it is possible to use concentrations of up to 99.5 percent or even pure active substance.

The active substances of the formula I can, for example, be formulated as follows: Dusts The following substances are used to manufacture (a) a 5 percent and (b) a 2 percent dust: v

a. 5 parts of active substance 95 parts of talcum b. 2 parts of active substance 1 part of highly disperse silica 97 parts of talcum. The active substances are mixed with the carriers and ground. Granules The following substances are used to produce 5% granules:

5 parts of active substance,

0.25 parts of epichlorohydrin,

0.25 parts of cetylpolyglycol ether,

3.50 parts of polyethylene glycol,

91 parts of kaolin (particle size 0.3 0.8 mm);

The activesubstance ismixed with epichlorohydrin and dissolved with 6 parts ofacetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on to kaolin, and the acetone subsequently evaporated in vacuo.

Wettable powder The following constituents are used for. the preparation of (a) a 40 percent, (b) and (d) a 10 percent wettable powder:

a. 40 parts of active substance,

5 parts of sodium lignin sulphonate,

1 part of sodium dibutyl-naphthalene sulphonate,

54 parts of silica acid.

b. 25 parts of active substance,

4.5 parts of calcium lignin sulphonate 1.9 partsof Champagne chalk/hydrox'yethyl cellulose mixture (1:1),

-'l.5 parts of sodium dibutyl naphthalene sulphonate',

parts of silica acid,

19.5 parts of Champagne chalk,

28.1 parts of kaolin.

c. 25 parts of active substance,

2.5 parts of -isooctylphenoxy-polyoxyethyleneethanol,

1,7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1),

8.3 parts of sodium aluminium silicate,

16.5 parts of kieselguhr,

46 parts of kaolin.

d. 10 parts of active substance,

3 parts of a mixture'of the sodium salts of saturated fatty alcohol sulphates,

5 parts of naphthalen condensate,

82 parts of kaolin.

The active substances are intimately mixed, in suit able mixers, with the additives, the mixture being then ground in the appropriate mills and rollers. Wettable powder are obtained which can be diluted with water to give suspensions of any desired concentration. Emulsifiable concentrates:

The following substances are used to produce (a) a 10 percent and (b) a 25 percentemu'lsifiable concentrate:

. From these concentrates it is possible to produce, by dilution with water, emulsion of any desired concentration.

c) a 25 percent and sulphonic acid/formaldehyde Spray:

The following constituents are used to prepare a percent spray:

5 parts of active substance,

1 part of epichlorohydrin,

94 parts of benzine (boiling limits 160 190C).

EXAMPLE 1 play ingest poison action against Spodoplera litoratis and Leptinotarsa decemlineala. 8. Systemic insecticidal action To determine the systemic action, rooted bean plants (Viciafabae) are put into a 0.01 percent aqueous active substance solution (obtained from a 10 percent emulsifiable concentrate). After 24 hours, aphids (Aphis fabae) are placed on the parts of the plant above the soil. The aphids are protected from contact and gas action by means ofa special device. The test is carried out at 24C and 70 percent relative humidity. In the above tests the compounds according to Example I displayed good insecticidal ingest poison action and systemic insecticidal action.

EXAMPLE 3 Action against Chilo suppressalis Six rice plants at a time of the variety Caloro were transplated into plastic pots (diameter at the top 17 cm) and reared to a height of about 60 cm. Infestation with Chilo suppressalis larvae (L 3-4 mm long) took place 2 days after application of the active substance in The following compounds are also manufactured in granule form to the paddy water (rate of application:

analogous manner:

8 kg of active substance per hectare). Evaluation of the insecticidal action took place 10 days after application of the granules.

The compounds according to Example 1 were active in the above test against Chilo suppressalis.

EXAMPLE 4 Action against soil insects Sterilised compost earth was homogeneously mixed substance so that there resulted a rate of application of 8 kg of active substance per hectare.

Young zucchetti plants (Cucumis peop) were put into plastic pots with the treated soil (3 plants per pot; diameter of pot 7 cm). Each pot was infected immediately aterwards with 5 Aulocophora femoralis and Pachmoda or Chortiphilia larvae. The control was carried out 4, 8, l6 and 32 days after depositing the larvae.

' At -100 percent kill after the first control, a fresh infestation with 5 larvae each was carried out in the ple I displayed action against Aulacophora fermralis,-

Pachmoda and Chlortophila larvae.

EXAMPLE Action against ticks A. Rhicephalus bursa.

In each of two test series 5 adult ticks and 50 tick larvae are counted into a glass tube and immersed for l to 2 minutes in 2 ml of an aqueous emulsion from an amulsion series each containing 100, 10, l and 0.1 ppm of test substance. The tube is then sealed with a standardised cotton wool plug and placed on its head, so that the active substance emulsion can be adsorbed by the cotton -wool.

In the case of the adults evaluation takes place after 2 weeks, and in that of the larvae after 2 days. Each test is repeated twice.

The compounds according to Example 1 act in the above test against adults and larvae of Rhicephalus bursa. B. Boophilus microplus (larvae) Tests are carried out in each case with 20 OP- sensitive larvae using analogous dilution series as in the case of test A. (The resistance relates to the tolerability of Diazinon).

The compounds according to Example 1 act in these tests against sensitive and OR resistant larvae of Boophilus microplus.

EXAMPLE 6 Acaracidal action Phaseolus vulgaris (dwarf beans) have an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test for the propyl, n-butyl, n-pentyl or C H OCH CH R reprelarvae, adults and eggs are evaluated after 7 days under a stereoscopic microscope and the result expressed in percentages. During the interim, the treated plants are kept in greenhouse compartments at 25C.

The compounds according to Example 1 are active in the above test against eggs, larvae and adults of Terranchus urticae.

EXAMPLE 7 In order to assess the nematocidal action, the galls.

present on the roots are counted 28 days after planting and sowing. The compounds according-to Example display good action against Meloidgyne Avenaria.

We claim: 1. A compound of the formula wherein R represents methyl or ethyl, R represents sents hydrogen, methyl or ethyl, R represents 'methyl or ethyl, X and X, each represents hydrogen or chlorine, and Y represents oxygen or sulphur.

2. Compounds according to claim 1, wherein R represents ethyl, R represents propyl, n-butyl, C 'H OCH CH or n-amyl, R and R each represents methyl or ethyl, X and X represent hydrogen or chlo- .rine and Y represents oxygen.

3. A compound according to claim 2 of the formula 4. A compound according to claim 2 of the formula C H O 5. A compound according, to claim 2 of the formula $0 M CH5 2 7. A compound according to claim 2 of the formula 19 I 20 8. A compound according to claim 1 of the formula 11. A compound according to claim 1 of the formula n C H S ll Cl 3 7 S c H P SO N(CH (MCBRIS I 2 5, C1 P-O -SO MCIL 9. a compound according to claim 1 of the formula S (n) C H S II 12. A compound according to claim I of the formula P- so N(C H i c H 2 2 5 2 S 10. A compound according to claim 1 of the formula 2 5 llZ 3L SO N(CH 0 H 

1. A COMPOUND OF THE FORMULA
 2. Compounds according to claim 1, wherein R represents ethyl, R1 represents propyl, n-butyl, C2H5OCH2CH2- or n-amyl, R2 and R3 each represents methyl or ethyl, X and X1 represent hydrogen or chlorine and Y represents oxygen.
 3. A compound according to claim 2 of the formula
 4. A compound according to claim 2 of the formula
 5. A compound according to claim 2 of the formula
 6. A compound according to claim 2 of the formula
 7. A compound according to claim 2 of the formula
 8. A compound according to claim 1 of the formula
 9. a compound according to claim 1 of the formula
 10. A compound according to claim 1 of the formula
 11. A compound according to claim 1 of the formula
 12. A compound according to claim 1 of the formula 